201211089 六、發明說明： 【交叉參考相關申請案】 本申請案請求2010年6月2曰申請的德國專利 申請號10 2010 022 464.2的優先權，基於所有有用 目的將其全體内容於此併入參考。 【發明所屬之技術領域】 本發明涉及以丁二酸丙酸酯為基質的可熱塑加 工之聚胺基曱酸酯。 【先前技術】 熱塑性聚胺基曱酸酯彈性體(TPUs)早已公知。 它們由於優越機械性能與已知便宜的熱塑加工性能 優點的組合而具有工業重要性。通過使用不同化學 構成組分可獲得機械性能的廣泛變化。TPUs的概 述、它們的性能和用途例如在Kunststoffe 68(1978) ’ 第 819-825 頁或 Kautschuk:，Gummi， Kunststoffe 35(1982)，第 568-584 頁中給出。 TPUs由線性多元醇，通常為聚酯或聚醚多元 醇、有機二異氰酸酯和短鏈二元醇（鏈增長劑）構 成。另外可加入催化劑加速生成反應。為了形成該 性能，構成組分可在相對寬的莫耳比内變化。已經 證實多元醇對鏈增長劑的莫耳比為1:1-1:12是合適 的。這導致產品在50肖氏A-75肖氏D的範圍内。201211089 VI. OBJECTS: [CROSS REFERENCE TO RELATED APPLICATIONS [0002] This application claims priority to the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the benefit of the entire disclosure of . TECHNICAL FIELD OF THE INVENTION The present invention relates to a thermoplastically processable polyamine phthalate based on succinic acid propionate. [Prior Art] Thermoplastic polyaminophthalate elastomers (TPUs) have long been known. They are of industrial importance due to the combination of superior mechanical properties and the advantages of known inexpensive thermoplastic processing properties. Extensive changes in mechanical properties can be obtained by using different chemical constituents. An overview of TPUs, their performance and uses are given, for example, in Kunststoffe 68 (1978) pp. 819-825 or Kautschuk:, Gummi, Kunststoffe 35 (1982), pp. 568-584. TPUs are composed of linear polyols, typically polyester or polyether polyols, organic diisocyanates, and short chain glycols (chain extenders). Alternatively, a catalyst may be added to accelerate the formation reaction. To form this property, the constituent components can be varied within a relatively wide molar ratio. It has been confirmed that the molar ratio of the polyol to the chain extender is from 1:1 to 1:12. This results in a product in the range of 50 Shore A-75 Shore D.
TPUs可連續或不連續製備。眾所周知的工業製 備方法為帶加工(GB 1057018 A)和擠出機加工(DE 4 1964834 A 和 DE 2059570 A)。 可以經由控制多元醇的方式形成多種性能組 合，當然良好的機械值對彈性體特別重要》聚醚多 元醇的使用賦予TPUs特別良好的水解性能。如果 想要具有良好機械性能，聚酯多元醇為有利的。 用於TPUs的聚酯多元醇例如由具有2·12個碳 原子，較佳為4-6個碳原子的二羧酸和多官能醇， 例如具有2-10個碳原子的二元醇製備，採用 500-5,000的聚酯分子量作為標準。如在同樣關於來 自聚酯多元醇的TPUs的ΕΡ 175 76 32 Α2中所記 載，提供具有特別良好穩定性的特別均勻成形製品 的TPUs為借助單體的特殊計量順序而獲得。 WO 2008/104541 A記載了由碳水化合物通過 發酵以生物學方式生產的丁二酸與至少雙官能醇得 到聚醋醇的反應。所選擇的雙官能醇為單乙二醇、 一乙一醇、單丙一醇、二丙二醇、1，4_丁二醇、 戊，醇、仏己二醇、孓曱基-U·丙二醇、3_曱基-1，5- 戊二醇、新戊二醇、丙三醇、三甲基丙二醇、新戊 :醇和山梨糖醇。基於以丙二醇的㈣醇未被提 =未提及對於聚g旨醇分子量的限制練佳範 此二、凊求保護了由這絲瞒製備的TPUs。在這 :::中1記載了分子量為約I900的丁二酸、己TPUs can be prepared continuously or discontinuously. Well known industrial preparation methods are belt processing (GB 1057018 A) and extruder processing (DE 4 1964 834 A and DE 2059570 A). A variety of performance combinations can be formed by controlling the polyol, although good mechanical values are of particular importance to the elastomer. The use of polyether polyols imparts particularly good hydrolysis properties to TPUs. Polyester polyols are advantageous if good mechanical properties are desired. The polyester polyol used for the TPUs is, for example, prepared from a dicarboxylic acid having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, and a polyfunctional alcohol such as a glycol having 2 to 10 carbon atoms. A molecular weight of 500-5,000 polyester is used as a standard. As noted in ΕΡ 175 76 32 Α 2, which is also related to TPUs from polyester polyols, TPUs which provide particularly uniform shaped articles having particularly good stability are obtained by means of a special metering sequence of monomers. WO 2008/104541 A describes the reaction of succinic acid, which is biologically produced by fermentation of a carbohydrate, with at least a bifunctional alcohol to obtain a polyhydric alcohol. The selected bifunctional alcohols are monoethylene glycol, monoethyl alcohol, monopropanol, dipropylene glycol, 1,4-butanediol, pentane, alcohol, hexanediol, decyl-U-propylene glycol, 3 _Mercapto-1,5-pentanediol, neopentyl glycol, glycerol, trimethylpropanediol, neopentyl: alcohol and sorbitol. Based on the fact that the (tetra) alcohol is not raised with propylene glycol. There is no mention of the limitation on the molecular weight of the alcohol for the polyg. Therefore, the TPUs prepared from this silkworm are protected. In this ::: 1 describes succinic acid with a molecular weight of about I900,
St醇和丁二醇的聚酯，並且使其反應得到 值的改^和平均機械值的TPUS。未發現機械 值的改進，並且耐撕裂擴展性甚至略有下降。 201211089 【發明内容】 本發明的目的為提供具有改進機械性能，例如 100%模量（ISO 527-1、-3)或耐撕裂擴展性（ISO 34-1)，並且可完全或部分由可以生物學方式生產的 組分製備的TPUs。 令人驚奇地，在一個具體實施例中，已經可以 通過具有50肖氏A-70肖氏D硬度(ISO 868)的可熱 塑加工之聚胺基曱酸酯彈性體達到這一目的，該彈 性體由包含以下物質的組分反應獲得： a) 一種或多種官能度為1.8-2.2的線性聚酯二元 醇，其中所述一種或多種線性聚酯二元醇包含 聚丁二酸 1，3-丙酸酯並且具有 l，950-4,000g/mol的平均分子量， b) 一種或多種有機二異氰酸@旨， c) 一種或多種分子量為60-350g/mol的二元醇， 其中所述組分的NC0:0H莫耳比為0.9:1-1.1:1。 本發明的另一具體實施例為具有50肖氏A-70 肖氏D硬度(ISO 868)的可熱塑加工之聚胺基曱酸酯 彈性體，其由包含以下物質的組分獲得： a) 一種或多種官能度為1.8-2.2且平均分子量為 2,000-3,500g/mol的線性聚酯二元醇，其中該一 種或多種線性聚酯二元醇包含由1，3_丙二醇、 丁二酸或其混合物構成並且由碳水化合物通過 發酵以生物學方式生產的聚丁二酸1，3-丙酸 酉旨， b) 一種或多種有機二異氰酸酯，選自4,4'-二苯基 6 曱烷二異氰酸酯、異佛爾酮二異氰酸酯、二環 己基曱烷-4,4-二異氰酸酯、1，6-六亞甲基二異 氰酸酯、1,5-伸萘基二異氰酸酯、及其混合物， c) 一種或多種鏈增長二元醇，選自1，4-丁二醇、 1，3-丙二醇、1,2-乙二醇、1，6-己二醇、1，4-二(β-羥乙基）氫醌、及其混合物， 其中所述組分的NCO:OH莫耳比為0.9:1-1.1:1。 本發明的另一具體實施例為生產上述可熱塑加 工之聚胺基曱酸酯彈性體的方法，其包括： A) 使一種或多種官能度為1.8-2.2的線性聚酯二 元醇與第一部分的一種或多種有機二異氰酸酯 以1.1:1-3.5:1的NCO:OH莫耳比反應，形成較 高重量的異氰酸酯封端預聚物，其中該一種或 多種線性聚酯二元醇包含聚丁二酸1,3-丙酸酯 並且具有l，950-4,000g/mol的平均分子量， B) 使在A中形成的較高重量異氰酸酯封端預聚物 與第二部分的一種或多種有機二異氰酸酯混 合，其中第一和第二部分有機二異氰酸酯的總 量為所用二異氰酸酯的總量，和 C) 使在B)中製備的混合物與一種或多種分子量 為60-350g/mol的二元醇反應。 發明詳述 “NCO:OH莫耳比’’在此表示異氰酸酯基b)對來 自a)和c)的對異氰酸酯基呈反應性的羥基之比率。 術語“平均分子量”在此和下文是指數量平均分 201211089 于量Mn。 —:用的有機二異氰酸酯b)例如為脂族、環脂 族、芳脂族、雜環和芳族二異氰酸酉旨，例如在JustusThe polyester of St alcohol and butylene glycol, and its reaction gives a change in value and a TPUS of the average mechanical value. No improvement in mechanical values was observed, and the tear propagation resistance was even slightly lowered. 201211089 SUMMARY OF THE INVENTION It is an object of the present invention to provide improved mechanical properties, such as 100% modulus (ISO 527-1, -3) or tear propagation resistance (ISO 34-1), and may be fully or partially TPUs prepared by biologically produced components. Surprisingly, in one embodiment, this has been achieved by a thermoplastically processable polyamine phthalate elastomer having a Shore A-70 Shore D hardness (ISO 868) of 50 Shore A, which The elastomer is obtained by reacting a component comprising: a) one or more linear polyester diols having a functionality of from 1.8 to 2.2, wherein the one or more linear polyester diols comprise polysuccinic acid 1, 3-propionate and having an average molecular weight of 1,950-4,000 g/mol, b) one or more organic diisocyanates, c) one or more glycols having a molecular weight of from 60 to 350 g/mol, wherein The NC0:0H molar ratio of the components is from 0.9:1 to 1.1:1. Another embodiment of the invention is a thermoplastically processable polyamine phthalate elastomer having a 50 Shore A-70 Shore D hardness (ISO 868) obtained from a component comprising: a a linear polyester diol having one or more functionalities of from 1.8 to 2.2 and an average molecular weight of from 2,000 to 3,500 g/mol, wherein the one or more linear polyester diols comprise 1,3 -propanediol, succinic acid Or a mixture thereof and consisting of polylactic acid 1,3-propionic acid produced by fermentation of a carbohydrate by fermentation, b) one or more organic diisocyanates selected from 4,4'-diphenyl 6 oxime Alkyl diisocyanate, isophorone diisocyanate, dicyclohexyldecane-4,4-diisocyanate, 1,6-hexamethylene diisocyanate, 1,5-anaphthyl diisocyanate, and mixtures thereof, c One or more chain-growth glycols selected from the group consisting of 1,4-butanediol, 1,3-propanediol, 1,2-ethanediol, 1,6-hexanediol, 1,4-bis(β-) Hydroxyethyl)hydroquinone, and mixtures thereof, wherein the components have an NCO:OH molar ratio of from 0.9:1 to 1.1:1. Another embodiment of the present invention is a process for producing the above thermoplastically processable polyaminophthalate elastomer comprising: A) one or more linear polyester diols having a functionality of from 1.8 to 2.2 The first portion of the one or more organic diisocyanates is reacted at a NCO:OH molar ratio of from 1.1:1 to 3.5:1 to form a higher weight isocyanate-terminated prepolymer, wherein the one or more linear polyester diols comprise Polysuccinic acid 1,3-propionate and having an average molecular weight of 1,950-4,000 g/mol, B) one or more of the higher weight isocyanate-terminated prepolymer formed in A and the second portion The organic diisocyanate is mixed, wherein the total amount of the first and second partial organic diisocyanates is the total amount of the diisocyanate used, and C) the mixture prepared in B) and the one or more molecular weights of 60-350 g/mol The alcohol reaction. DETAILED DESCRIPTION OF THE INVENTION "NCO: OH molar ratio" here denotes the ratio of isocyanate groups b) to hydroxyl groups which are reactive toward isocyanate groups from a) and c). The term "average molecular weight" here and below means the amount The average amount is 201211089 in the amount of Mn. -: The organic diisocyanate b) used is, for example, aliphatic, cycloaliphatic, araliphatic, heterocyclic and aromatic diisocyanate, for example in Justus
Liebigs Annalen der 泌，第 75 i36 頁中所 記載的。 可特別提及以下實例：脂族二異氰酸§旨類，例 如八亞曱基二異氰酸酯，環脂族二異氰酸酯類，例 如異佛爾酮二異氰酸酯、M-環己烷二異氰酸酯、 1-曱基-2,4-環己院二異氰酸酯和丨曱基_2,6_環己烧 二異氰酸酯及其相應異構體混合物、4，[二環己基 曱烷二異氰酸酯、2,4，_二環己基曱烷二異氰酸酯和 2,2’-二環己基曱烷二異氰酸酯及其相應異構體混合 物，芳族二異氰酸酯類，例如2,4_伸甲苯基(t〇luyiene) 一異氰酸酯、2,4-伸曱苯基二異氰酸酯和2,6-伸曱苯 基二異氰酸酯的混合物、4,4，-二苯基曱烷二異氰酸 醋、2,4’-二苯基曱烷二異氰酸酯和2,2,二苯基甲烷二 異氰酸酯、2,4，-二苯基甲烷二異氰酸酯和4,4，·二苯 基甲燒二異氰酸酯的混合物、胺基曱酸酯改性的液 體4,4’·二苯基曱烷二異氰酸酯或2,4··二苯基甲烷二 異氰酸酯、4,4，-二異氰酸根合-1，2-二苯基乙烷和1，5· 伸萘基二異氰酸酯。較佳使用丨，6_六亞曱基二異氰 酸酯、1，4-環己烷二異氰酸酯、異佛爾酮二異氰酸 酯、二環己基甲烷二異氰酸酯、4,4，-二苯基甲烷二 異氰酸酯含量為大於96重量％的二苯基曱烷二異氰 酸酯異構體混合物、4,4'-二苯基曱烷二異氰酸酯和 1，5-伸萘基二異氰酸酯。可單獨或以彼此混合物形 8 式使用提到的二異氰酸酯。它們還可與至多15莫耳 %(以二異氰酸酯總量計算）的多異氰酸酯一起使 用，然而多異氰酸酯應該至多以仍可形成熱塑性可 加工產品的量加入。多異氰酸酯的實例為三苯基曱 烷_4,4’，4”-三異氰酸酯和多苯基多亞曱基多異氰酸 酉旨。 採用線性聚酯二元醇作為多元醇。由於生產， 這些常常包含少量非線性化合物。因此還常常稱為 “基本線性多元醇”。 本發明採用的聚酯二元醇或一些聚酯二元醇的 混合物a)由40-100重量％，較佳是由90-100重量％ 的丁二酸和1，3-丙二醇構成，重量％值基於所採用 聚酉旨二元醇的總重量。 聚酯二元醇例如可由具有2-12個碳原子，較佳 為4-6個碳原子的二羧酸與多官能醇製備。可用的 二羧酸例如為：脂族二羧酸類，例如丁二酸、戊二 酸、己二酸、辛二酸、壬二酸和癸二酸，或芳族二 羧酸類，例如鄰苯二曱酸、間苯二曱酸和對苯二曱 酸。二羧酸可單獨或作為混合物，例如以丁二酸、 戊二酸和己二酸混合物形式使用。對於聚酯二元醇 的製備，可有利地使用相應的二羧酸衍生物代替二 羧酸，例如醇基中具有1_4個碳原子的羧酸二酯類， 例如對苯二曱酸二曱酯或己二酸二曱酯，羧酸酐 類，例如丁二酸酐、戊二酸酐或鄰苯二甲酸酐，或 羧酸醯氯類。多官能醇的實例為具有2-10個，較佳 2-6個碳原子的二元醇類，例如乙二醇、二乙二醇、 201211089 1，4-丁二醇、1，5-戊二醇、1，6-己二醇、1，10-癸二醇、 2,2-二曱基-1，3-丙二醇、1，3-丙二醇、2-曱基-1,3-丙 二醇、3-曱基-1，5-戊二醇或二丙二醇。 此外，還可同時使用少量的至多全部反應混合 物的3重量％的具有較高官能度的低分子量多元 醇，例如1，1，1-三羥曱基丙烷或新戊四醇。 較佳為僅使用雙官能起始化合物。 例如如果採用二羧酸的二曱酯，結果為可能發 生由於不完全酯交換，少量未反應的曱酯端基使聚 酯的官能度降至低於2.0，例如至1.95或至1.90。 縮聚通過本領域熟習該項技藝者已知的途徑進 行，例如通過最初在標準壓力或輕微減壓下，在 150-270°C的溫度下排出反應水，並且隨後緩慢降低 壓力，例如降至5-20毫巴。原則上催化劑不是必需 的，然而通常非常有幫助。例如，錫(II)鹽、鈦(IV) 化合物、鉍(III)鹽等可用於此。 此外可有利地使用惰性傳輸氣體，例如氮氣排 出反應水。除此之外，還可使用這樣的方法，其中 在共沸酯化中採用室溫下為液體的傳輸劑如曱苯。 通常對於TPUs的合成僅採用一種基本線性聚 酯二元醇。然而，也可以使用多於一種基本線性聚 酯二元醇的混合物。 如上，基於所採用的全部聚酯二元醇，聚酯二 元醇、視情況一些聚酯二元醇的混合物，包含40-100 重量％，較佳90-100重量％的聚丁二酸1,3-丙酸酯。 聚丁二酸1,3-丙酸酯由丁二酸和1,3-丙二醇構成。 丁二酸可通過石油化學途徑製備，例如採用馬 來酸作為起始化合物，或可以來源於生物源。 如果採取生物源，通過發酵由微生物途徑轉化 為丁二酸的碳水化合物，例如在US-A 5,869,301中 所記載者是可用的。 1，3-丙二醇同樣可以通過石油化學途徑製備， 例如採用丙烯醛作為起始化合物，或可以來源於生 物源。因而，例如1,3_丙二醇在Dupont Tate & Lyle 由玉米漿以發酵方式在大的工業規模獲得。 較佳聚酯二元醇使用至少9〇重量％之以生物為 基質的丁二酸(基於所採用羧酸或丁二酸的總重量） 和/或至少90重量❶/〇之以生物為基質的1，3-丙二醇 (基於所採用二元醇或丙二醇的總重量）製備。 根據本發明，聚酯二元醇具有 l，95(M，000g/m〇b 較佳為 2 〇〇〇 3 5〇〇g/m〇卜特佳 為2，l〇〇_3,〇〇〇g/mol ’並且非常特佳為 2,200-2,900g/mol的數量平均分子量一〆 所採用的鏈增長劑為二元醇類，視情況在與少 量一胺的混合物中，分子量為60-350g/mol,較佳為 具有2_14個碳原子的脂族二元醇類，例如乙二醇、 1,3丙—醇、ι，6_己二醇、二乙二醇、二丙二醇、乙 二醇，尤其是1，4-丁二醇。然而，同樣合適的為對 苯一曱酸與具有2-4個碳原子二元醇的二酯類，例 如對笨一甲酸雙乙二醇或對苯二甲酸雙1，4-丁二醇 日氫職的說基亞貌基趟類，例如1，4_二 乙基）氫醌，乙氧基化雙酚類，例如1,4-二(β-羥乙基) 201211089 雙^ A。較佳地」使用乙二醇、1，3-丙二醇、1，4-丁 一醇、1，6-己二醇和认二(卜經乙基)氫酿作為鍵增 長劑°還可&用上述璉增長劑的混合物。此外，還 可加入相對少量的三元醇。 此外還可添力π少量傳統單官能化合物 ，例如鍵 終止劑或脫模助劑。可提及以下㈣：_，例如 辛醇和硬醇’或胺類，例如了胺和硬脂胺。 對於TPUs的製備，視情況在催化劑、助劑物 質和/或添加_存在下，使構成組分以這樣的量反 應’，得NCO基團與sNC〇呈反應性的基團總和 的當量比為0.9:1.0-1.1:1.〇 ，較佳為 0.95:l.〇-l.i〇:i.〇 。 本發明合適的催化劑為根據現有技術已知和傳 統的三級胺類，例如三乙胺、二曱基環己基胺、 曱基嗎啉、N，N’-二甲基哌畊、2_(二甲基胺基乙氧基) 乙醇、一氮雜雙環[2,2,2]辛烧和類似化合物，尤其 是有機金屬化合物，例如鈦酸酯、鐵化合物或錫化 合物，例如二乙酸錫、二辛酸錫、二月桂酸錫或脂 族羧酸的二烷基錫鹽，例如二乙酸二丁基錫或二月 桂酸二丁錫或類似化合物。較佳的催化劑為有機金 屬化合物，尤其是鈦酸酯以及鐵和錫化合物。基於 TPU，催化劑在TPUS中的總量通常為約〇·5重量 %，較佳為0-1重量％。 除TPU組分和催化劑之外，還可以加入助劑物 質和/或添加劑。可提及以下實例：潤滑劑，例如脂 肪酸酯、其金屬皂、脂肪酸醯胺、脂肪酸酯醯胺和 12 矽化合物，防黏連劑，抑制劑，抗水解、光、熱和 脫色之穩定劑，防火劑，染料’顏料，無機和/或有 機填料以及增強劑。增強劑尤其為纖維增強物質， 例如無機纖維，其根據現有技術製備並且充滿浸潤 劑。較佳地，還可將奈米微粒固體，例如碳黑以0-10 重量％的量加入TPUs中。關於提及的助劑物質和添 加劑的更多細節在技術文獻有描述’例如J.H. Saunders 和 K.C. Frisch 的專題論文“High Polymers (高聚物）”，第XVI卷，聚胺基曱酸酯，第1和2 部分，Verlag Interscience Publishers，1962 和 1964， R. GSchter 和 H. Mtiller 的 Taschenbuch ftir Kunststoff-Additive(Hanser Verlag Munich 1990)或 DE-A 29 01 774。 可併入TPU的其他添加劑為熱塑性塑膠’例如 聚碳酸酯和丙烯腈/丁二烯/苯乙烯三元共聚物’尤其 是ABS。還可使用其他彈性體，例如橡膠、乙烯/ 醋酸乙烯酯共聚物、笨乙烯/丁二烯共聚物和其他 TPUs。市售的塑化劑，例如磷酸酯、鄰苯二曱酸酯、 己二酸酯、癸二酸酯和燒基續酸酯也適合併入。 TPU可以在一步中（同時加入反應組分=單次） 或在多步中（例如預聚物方法或根據EP 571 830包 括柔胜鏈段預增長的方法)製備。 在較佳的具體實施例中，TPU以包括柔性鏈段 預增長的多步方法製備，其中 在這一方法的步驟A)中，一種或多種官能度為 1.8-2.2的線性聚酯二元醇與份量1的有機二異氰醆 201211089 醋以 1.1:1-3.5:1，，佳 U:1_2.5:1 的 nc〇:〇h 莫耳 比反應’形成較咼重量的異氰酸酯封端預聚物 (“NCO予頁聚物，，）’其中該一種或多種線性聚酿二元 醇包含聚丁』U-丙酸醋並且平均分子量為 1,950-4,000g/mol * 在步驟B)中，使步驟A中形成的腳預聚物 與份量2的有機二異氰_旨混合，其中份量i和2 的總和等於所用二異氰酸酯的總量，和 在步驟〇中，使步驟B)中製備的混合物與一種 或多種分子量為60-350g/mol的二元醇反應。 較佳為㈣A)t份量丨的所述-種❹種 氰酸醋與步驟B)中份量2的二錢㈣相同。、 獨立於該方法，在所有步驟 〇H基團的莫耳比設定為〇9:1_1ι:ι。土图對、，息 此、【：的f合裝置，較佳為以高剪切能運行的那 丘製備TPUs。對於連續製備，可提及實例 /較佳為擠出機，例如雙螺杆擠出機和 布氏(Buss)捏合機、或靜態混合器。 動鞋可加工為注模塑製品，例如運 膜。 ％。卩件’以及均勻擠出製品，尤其是薄 加二ί有改進的機械值’例如在拉伸試驗中增 加的模量和改進的耐撕裂擴展性。 整體目的，如上所述的所有參考文獻 儘管已經顯#記载了 S些特定結構來體現本 201211089 發明，對於本領域熟習該項技藝者顯而易見的是可 進行該部分的各種改性和重排而不脫離基礎發明構 思的精神和範圍’而且不限於本文所顯示和記載的 特殊形式。 借助以下實施例更詳細地解釋本發明。 【實施方式】 實施例 A) 所用原材料： PE 225 B 分子量為 Mn=2,200g/mol 的丁 二醇己二酸醋(Bayer MaterialScience AG) MDI 二苯基曱烷-4,4’·二異氰酸酯 (Bayer MaterialScience AG) BUT 1，4-丁二醇(BASF AG) 1，3-丙二醇， 生物基(DuPont Tate & Lyle) 丁二酸， 生物基，酸值：946 mg KOH/g ’ 對應 Mn=118.6g/mol(Bioamber) B) 聚酯的製備： BSP 1100 分子量為 Kin=l,100g/mol 的聚 丁二酸1，3-丙酸酉旨 BSP 2200 分子量為砑n=2,200g/mol的聚 丁二酸1，3-丙酸酉旨 BSP2900 分子量 gnn=2,900g/mol 的聚 丁二酸1,3-丙酸酯 BSP 1100 首先在室溫下、同時在用氮氣層覆蓋下，將 15 201211089 2,421g(20.41m〇l)生物基丁 二酸和 1，817g(23.87mol) 1，3-丙二醇引入裝備有蕈形加熱器 (heating mushroom)、機械攪拌器、内部溫度計、4〇cm 填充柱、柱頭、下行強化冷凝器和膜式真空泵的6 升4頸燒瓶中，並且在攪拌下緩慢加熱至2〇〇π， 從約140°C的溫度蒸出反應水。在約处後，停止反 應。加入70mg二水合氣化錫(π),在約2h的時間 内使壓力降至200毫巴’並且在這些條件下進一步 繼續反應16小時。為了使反應完全，將真空降至 16毫巴持續另外4h，冷卻混合物，並且測得以下數 據： 聚醋BSP 1100的分析：經值：104.1 mg KOH/g ;酸值：0.22 mg KOH/g ;黏度： ll,800mPas(25〇C) 、 l,470mPas(50〇C) 、 405mPas(75°C)。 OH 值和酸值按照在“Methoden der organischen Chemie (有機化學方法）（Houben-Weyl)， Makromolekulare Stoffe (大分子物質），第 14/2 卷， 第 17 頁 ’ Georg Thieme Verlag，Stuttgart 1963 中記 載的進行測定。 黏度用來自Anton Paar的裝備有CP-50-1測量 錐的Physica MCR 51黏度計以l-l，000/s的剪切速 率測定。 BSP 2200 [b)]和 BSP 2900 [c)]與 BSP 1100 類似 製備，改變二羧酸對二元醇的莫耳比以確定聚酯多 元醇的分子量。 b) BSP 2200 1，3-丙二醇的重量：3,776g(49.7mol) 丁二酸的重量：5,437g(45.8mol) 二水合氣化錫(II)的重量：270mg 聚醋的分析：經值：51.4 mg KOH/g ;酸值：0.4 mgKOH/g ;黏度：i，660mPas(75〇C) c) BSP 2900 1，3·丙二醇的重量：3,743g(49.25mol) 丁一酸的重量：5,493g(46.32mol) 一水合氯化錫(II)的重量：180mg 聚酯的分析：羥值：38.9 mg KOH/g ;酸值：0.9 mgKOH/g ;黏度：3,2i〇mPas(75〇c) C.TPUs的製備 在母種情況下，首先將表1中的一種多元醇引 入反應容器。加熱至18〇它後，在攪拌下加入份量j 的4,4’·二苯基曱烷二異氰酸醋(MDI)，並且借助基 於多元醇的量為5〇ppm的催化劑雙辛酸錫，使預聚 物反應達到轉化率基於多元醇為大於90莫耳0/〇。 當反應結束後，在攪拌下加入份量2的MDI。 然後加入表1中所示量的鏈增長劑丁二醇[BUT]， 各組分的NCO/OH比為L〇〇。㊣烈充分混合後，將 TPU反應混合物傾倒至金屬薄片上並且在12〇它下 調卵30分鐘。 201211089 表1 實施例 多元醇 多元醇的量 fmol] MDI份量 lfmoll MDI份量2 [mol] BUT [mol] 1 BSP2200 1 2.78 0.94 3.72 2* PE 225 B 1 2.78 0.94 3.72 3 BSP2200 1 2.85 1.50 4.35 4* BSP1100 1 2.78 0.06 1.88 5* PE 225 B 1 2.85 1.50 4.35 6 BSP2200 1 3.23 3.07 6.30 7* PE 225 B 1 3.23 3.07 6.30 8 BSP2200 1 3.51 3.87 7.38 9* PE 225 B 1 3.51 3.87 7.38 10 BSP2900 1 2.00 3.41 5.41 *非根據本發明的對比實施例 將澆鑄片材切斷並且造粒。使粒料在來自 Arburg的Allrounder 470 S(30-螺杆）注塑機中融化 並且成形為S1棒條(模具溫度：25°C ;棒條尺寸： 115x25/6x2)、薄材（模具溫度：25°C ;尺寸： 125x5〇x2mm)或圓塞(模具溫度：25°C ;直徑30mm， 厚度6mm)。 測量 硬度的測量根據ISO 868進行；在根據ISO 527-1、-3的拉伸試驗中測量得到100%模量、撕裂 強度和伸長率；根據ISO 34-1測量耐撕裂擴展性。 通過在直接從模具移出後（約3秒）的圓塞上測 量硬度，作為初始硬度，測量直接注模後的固化速 度。 這一值越高，注模中的固化速度越高而週期時 間越短。 201211089Liebigs Annalen der, pp. 75 i36. Mention may in particular be made of the following examples: aliphatic diisocyanates, such as octadecyl diisocyanate, cycloaliphatic diisocyanates, for example isophorone diisocyanate, M-cyclohexane diisocyanate, 1- Mercapto-2,4-cyclohexyl diisocyanate and mercapto 2,6-cyclohexene diisocyanate and their corresponding isomer mixtures, 4, [dicyclohexyldecane diisocyanate, 2,4,_ Dicyclohexyldecane diisocyanate and 2,2'-dicyclohexyldecane diisocyanate and mixtures of their corresponding isomers, aromatic diisocyanates, for example 2,4-tolylyi-isocyanate, a mixture of 2,4-extended phenyl diisocyanate and 2,6-extended phenyl diisocyanate, 4,4,-diphenyldecane diisocyanate, 2,4'-diphenylnonane Mixture of diisocyanate and 2,2,diphenylmethane diisocyanate, 2,4,-diphenylmethane diisocyanate and 4,4,diphenylmethane diisocyanate, amino phthalate modified liquid 4,4'·diphenyldecane diisocyanate or 2,4··diphenylmethane diisocyanate, 4,4,-diisocyanato-1,2-diphenylethane And 1,5· anthranyl diisocyanate. Preferably, ruthenium, 6-6 hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, 4,4,-diphenylmethane diisocyanate content It is more than 96% by weight of a mixture of diphenylnonane diisocyanate isomers, 4,4'-diphenyldecane diisocyanate and 1,5-anaphthyl diisocyanate. The diisocyanates mentioned may be used singly or in the form of a mixture of one another. They can also be used with up to 15 mole % (calculated as the total amount of diisocyanate) of polyisocyanate, however the polyisocyanate should be added at most in an amount which still forms the thermoplastic processable product. Examples of polyisocyanates are triphenyldecane-4,4',4"-triisocyanate and polyphenylpolyarylene polyisocyanate. Linear polyester diols are used as polyols. Due to production, These often contain small amounts of non-linear compounds and are therefore often referred to as "essentially linear polyols." The polyester diols used in the present invention or mixtures of some polyester diols a) are from 40 to 100% by weight, preferably It is composed of 90-100% by weight of succinic acid and 1,3-propanediol, and the weight % value is based on the total weight of the polyhydric diol used. The polyester diol may have, for example, 2 to 12 carbon atoms. It is preferably prepared from a dicarboxylic acid having 4 to 6 carbon atoms and a polyfunctional alcohol. Useful dicarboxylic acids are, for example, aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, hydrazine. Diacids and sebacic acids, or aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid and terephthalic acid. Dicarboxylic acids may be used singly or as a mixture, for example, succinic acid, pentane Used in the form of a mixture of acid and adipic acid. For the preparation of polyester diols, the corresponding The carboxylic acid derivative replaces a dicarboxylic acid such as a carboxylic acid diester having 1 to 4 carbon atoms in the alcohol group, such as dinonyl or decanoic acid adipate, a carboxylic acid anhydride such as succinic anhydride , glutaric anhydride or phthalic anhydride, or ruthenium chloride carboxylic acid. Examples of polyfunctional alcohols are diols having 2 to 10, preferably 2 to 6 carbon atoms, such as ethylene glycol, Ethylene glycol, 201211089 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimercapto-1,3-propanediol , 1,3-propanediol, 2-mercapto-1,3-propanediol, 3-mercapto-1,5-pentanediol or dipropylene glycol. In addition, a small amount of up to 3% by weight of the total reaction mixture can be used simultaneously. A low molecular weight polyol having a higher functionality, such as 1,1,1-trihydroxydecylpropane or neopentyl alcohol. It is preferred to use only a difunctional starting compound. For example, if a dicarboxylic acid is used Ester, the result is that due to incomplete transesterification, a small amount of unreacted oxime end groups reduces the functionality of the polyester to below 2.0, for example to 1.95 or to 1.90. Polycondensation is well known in the art. The route known to the skilled person is carried out, for example, by initially discharging the reaction water at a standard pressure or a slight reduced pressure at a temperature of from 150 to 270 ° C, and then slowly reducing the pressure, for example to 5-20 mbar. In principle, a catalyst is not essential, but it is usually very helpful. For example, a tin (II) salt, a titanium (IV) compound, a cerium (III) salt or the like can be used for this. Furthermore, it is advantageous to use an inert transport gas such as nitrogen to remove the reaction. In addition to this, it is also possible to use a method in which a liquid-transporting agent such as toluene is used in azeotropic esterification. Usually, only one substantially linear polyester diol is used for the synthesis of TPUs. However, it is also possible to use a mixture of more than one substantially linear polyester diol. As above, based on all polyester diols used, polyester diols, and optionally mixtures of polyester diols, comprise from 40 to 100% by weight, preferably from 90 to 100% by weight, of polysuccinic acid 1 , 3-propionate. Polysuccinic acid 1,3-propionate consists of succinic acid and 1,3-propanediol. Succinic acid can be prepared by a petrochemical route, for example using maleic acid as a starting compound, or can be derived from a biological source. If a biological source is employed, it is converted to a carbohydrate of succinic acid by fermentation by a microbial pathway, such as that described in US-A 5,869,301. The 1,3-propanediol can likewise be prepared by a petrochemical route, for example using acrolein as the starting compound or it can be derived from a biological source. Thus, for example, 1,3_propanediol is obtained in a large industrial scale by fermenting of Dupont Tate & Lyle from corn syrup. Preferably, the polyester diol uses at least 9% by weight of bio-based succinic acid (based on the total weight of the carboxylic acid or succinic acid used) and/or at least 90% ❶/〇 of the biological substrate. The 1,3-propanediol (based on the total weight of the glycol or propylene glycol employed) is prepared. According to the present invention, the polyester diol has 1,95 (M,000 g/m 〇 b is preferably 2 〇〇〇 3 5 〇〇 g/m 〇 为 2 2, 〇〇 3 3, 〇〇 〇g/mol ' and very particularly preferably a number average molecular weight of 2,200-2,900 g/mol. The chain extender used is a diol, optionally in a mixture with a small amount of a monoamine, having a molecular weight of 60-350 g. /mol, preferably an aliphatic diol having 2 to 14 carbon atoms, such as ethylene glycol, 1,3 propanol, iota, 6-hexanediol, diethylene glycol, dipropylene glycol, ethylene glycol , especially 1,4-butanediol. However, equally suitable are diesters of p-benzoic acid and diols having 2 to 4 carbon atoms, such as bis-ethylene glycol or p-benzene. Di-1,4-butanediol dihydrogen hydrides, such as 1,4-diethylhydroquinone, ethoxylated bisphenols, such as 1,4-di(beta) -Hydroxyethyl) 201211089 Double ^ A. Preferably, ethylene glycol, 1,3-propanediol, 1,4-butanol, 1,6-hexanediol, and di-(diethyl) hydrogen are used as the bond growth agent. A mixture of the above sputum growth agents. In addition, a relatively small amount of triol can be added. In addition, a small amount of conventional monofunctional compounds such as a bond terminator or a release aid can be added. The following (iv) may be mentioned: _, such as octanol and a hard alcohol' or an amine such as an amine and stearylamine. For the preparation of TPUs, the composition component is reacted in such an amount in the presence of a catalyst, an auxiliary substance and/or an additive _, and the equivalent ratio of the total group of the NCO group reactive with sNC〇 is 0.9: 1.0-1.1:1.〇, preferably 0.95: l.〇-li〇: i.〇. Suitable catalysts according to the invention are tertiary amines known from the prior art and conventional, such as triethylamine, dinonylcyclohexylamine, decylmorpholine, N,N'-dimethylpiped, 2_(two Methylaminoethoxy)ethanol, monoazabicyclo[2,2,2]octane and similar compounds, especially organometallic compounds such as titanates, iron compounds or tin compounds, such as tin diacetate, A tin dialkyl tin salt of tin octoate, tin dilaurate or an aliphatic carboxylic acid, such as dibutyltin diacetate or dibutyltin dilaurate or the like. Preferred catalysts are organic metal compounds, especially titanates and iron and tin compounds. The total amount of the catalyst in the TPUS is usually about 5% by weight, preferably 0-1% by weight, based on the TPU. In addition to the TPU component and the catalyst, auxiliary materials and/or additives may be added. The following examples may be mentioned: lubricants such as fatty acid esters, metal soaps thereof, fatty acid decylamines, fatty acid esters decylamine and 12 hydrazine compounds, anti-blocking agents, inhibitors, hydrolysis resistance, light, heat and decolorization stability Agents, fire retardants, dyes' pigments, inorganic and/or organic fillers and reinforcing agents. The reinforcing agent is especially a fiber-reinforced material, such as an inorganic fiber, which is prepared according to the prior art and is filled with an infiltrant. Preferably, nanoparticulate solids, such as carbon black, may also be added to the TPUs in an amount of from 0 to 10% by weight. Further details on the auxiliaries and additives mentioned are described in the technical literature 'for example, JH Saunders and KC Frisch's monograph "High Polymers", Volume XVI, Polyamine phthalates, Parts 1 and 2, Verlag Interscience Publishers, 1962 and 1964, R. GSchter and H. Mtiller, Taschenbuch ftir Kunststoff-Additive (Hanser Verlag Munich 1990) or DE-A 29 01 774. Other additives that may be incorporated into the TPU are thermoplastics such as polycarbonate and acrylonitrile/butadiene/styrene terpolymers, especially ABS. Other elastomers such as rubber, ethylene/vinyl acetate copolymers, stupid ethylene/butadiene copolymers, and other TPUs may also be used. Commercially available plasticizers such as phosphates, phthalates, adipates, sebacates and decanoates are also suitable for incorporation. The TPU can be prepared in one step (simultaneous addition of reaction components = single pass) or in multiple steps (e.g., a prepolymer process or a method of pre-growth according to EP 571 830 including a soft-segment segment). In a preferred embodiment, the TPU is prepared in a multi-step process comprising a pre-growth of flexible segments, wherein in step A) of the process one or more linear polyester diols having a functionality of from 1.8 to 2.2 Isocyanate-terminated prepolymerization with a weight of 1 part of organic diisocyanide 201211089 vinegar with 1.1:1-3.5:1, good U:1_2.5:1 nc〇:〇h molar ratio reaction ("NCO prepolymer,") wherein the one or more linear polyglycerols comprise polybutylene U-propionic acid vinegar and have an average molecular weight of 1,950-4,000 g/mol * in step B) The foot prepolymer formed in the step A is mixed with the portion 2 of the organic diisocyanate, wherein the sum of the parts i and 2 is equal to the total amount of the diisocyanate used, and in the step ,, the mixture prepared in the step B) Reacting with one or more glycols having a molecular weight of 60-350 g/mol. Preferably, (4) A) t parts of the amount of the quinone cyanide vinegar is the same as the amount 2 of the second step (4) in the step B). In this method, the molar ratio of the 基H group is set to 〇9:1_1ι:ι at all steps. The soil map is right, the interest ratio, the [: f fit It is preferred to prepare TPUs in the hills which are operated with high shear energy. For continuous preparation, mention may be made of examples/preferably extruders, such as twin-screw extruders and Buss kneaders, or static mixing. The moving shoes can be processed into injection molded articles, such as film transporting. %. 卩 ' and evenly extruded products, especially thin plus ί have improved mechanical values' such as increased modulus in tensile tests and Improved tear propagation resistance. Overall object, all references as described above, although the specific structure has been described to reflect the invention of 201211089, it will be apparent to those skilled in the art that this portion can be performed. The various modifications and rearrangements of the present invention are not limited to the spirit and scope of the basic inventive concept, and are not limited to the specific forms shown and described herein. The invention is explained in more detail by the following examples. [Embodiment] Example A) Raw material: PE 225 B Butanediol adipic acid vinegar with a molecular weight of Mn = 2,200 g/mol (Bayer MaterialScience AG) MDI Diphenylnonane-4,4'·diisocyanate (Bayer MaterialScience AG) B UT 1,4-butanediol (BASF AG) 1,3-propanediol, bio-based (DuPont Tate & Lyle) succinic acid, bio-based, acid value: 946 mg KOH/g ' Corresponding Mn = 118.6 g/mol (Bioamber) B) Preparation of polyester: BSP 1100 Polybutylene succinate with a molecular weight of Kin = 1,100 g/mol BSP 2200 Polyethylene succinate with molecular weight 砑n=2,200 g/mol 1,3-propionic acid hydrazine BSP2900 Poly(succinic acid 1,3-propionate BSP 1100 with molecular weight gnn=2,900 g/mol Firstly, at room temperature, while covering with a nitrogen blanket, 15 201211089 2,421 g ( 20.41m〇l) bio-based succinic acid and 1,817g (23.87mol) 1,3-propanediol were introduced with a heating mushroom, mechanical stirrer, internal thermometer, 4〇cm packed column, stigma, The mixture was cooled in a 6-liter 4-necked flask of a condenser and a membrane vacuum pump, and slowly heated to 2 〇〇π with stirring, and the reaction water was distilled off from a temperature of about 140 °C. After the appointment, stop the reaction. 70 mg of tin (dioxide) dihydrate was added, and the pressure was lowered to 200 mbar in a period of about 2 hours and the reaction was further continued under these conditions for 16 hours. To complete the reaction, the vacuum was reduced to 16 mbar for an additional 4 h, the mixture was cooled and the following data was determined: Analysis of the polyacetic acid BSP 1100: value: 104.1 mg KOH/g; acid value: 0.22 mg KOH/g; Viscosity: ll, 800mPas (25〇C), l, 470mPas (50〇C), 405mPas (75°C). The OH value and the acid value are described in "Methoden der organischen Chemie" (Houben-Weyl), Makromolekulare Stoffe (Molecular Substance), Vol. 14/2, p. 17 'Georg Thieme Verlag, Stuttgart 1963 The viscosity was determined using a Physica MCR 51 viscometer equipped with a CP-50-1 measuring cone from Anton Paar at a shear rate of ll,000/s. BSP 2200 [b)] and BSP 2900 [c)] BSP 1100 was prepared similarly, changing the molar ratio of dicarboxylic acid to diol to determine the molecular weight of the polyester polyol. b) BSP 2200 Weight of 1,3-propanediol: 3,776 g (49.7 mol) Weight of succinic acid: 5,437g (45.8mol) Weight of tin (II) dihydrate: 270mg Analysis of polyester: value: 51.4 mg KOH / g; acid value: 0.4 mgKOH / g; viscosity: i, 660 mPas (75 ° C) c) Weight of BSP 2900 1,3·propanediol: 3,743 g (49.25 mol) Weight of butyric acid: 5,493 g (46.32 mol) Weight of tin (II) chloride monohydrate: 180 mg Analysis of polyester: hydroxyl value: 38.9 mg KOH/g; acid value: 0.9 mgKOH/g; viscosity: 3,2i〇mPas (75〇c) Preparation of C.TPUs in the case of parent species, first A polyol in Table 1 was introduced into the reaction vessel. After heating to 18 Torr, a portion of 4,4'-diphenyldecane diisocyanate (MDI) was added with stirring, and with the aid of a polyol-based The amount of 5 〇ppm catalyst tin bis octylate, the prepolymer reaction to achieve conversion based on polyol is greater than 90 mol 0 / 〇. When the reaction is over, add 2 parts of MDI with stirring. Then add to Table 1. The indicated amount of chain extender butanediol [BUT], the NCO/OH ratio of each component is L〇〇. After vigorously mixing, the TPU reaction mixture is poured onto the metal flakes and the eggs are adjusted at 12°. 201211089 Table 1 Example The amount of polyol polyol fmol] MDI part lfmoll MDI part 2 [mol] BUT [mol] 1 BSP2200 1 2.78 0.94 3.72 2* PE 225 B 1 2.78 0.94 3.72 3 BSP2200 1 2.85 1.50 4.35 4 * BSP1100 1 2.78 0.06 1.88 5* PE 225 B 1 2.85 1.50 4.35 6 BSP2200 1 3.23 3.07 6.30 7* PE 225 B 1 3.23 3.07 6.30 8 BSP2200 1 3.51 3.87 7.38 9* PE 225 B 1 3.51 3.87 7.38 10 BSP2900 1 2.00 3.41 5.41 *The cast sheet is not cut according to a comparative example of the invention And granulation. The pellets were melted in an Allrounder 470 S (30-screw) injection molding machine from Arburg and formed into S1 rods (mold temperature: 25 ° C; rod size: 115x25/6x2), thin material (mold temperature: 25°) C; size: 125x5〇x2mm) or round plug (mold temperature: 25 ° C; diameter 30 mm, thickness 6 mm). Measurement of hardness was carried out according to ISO 868; 100% modulus, tear strength and elongation were measured in a tensile test according to ISO 527-1, -3; tear propagation resistance was measured according to ISO 34-1. The hardness after direct injection molding was measured by measuring the hardness on a round plug immediately after being removed from the mold (about 3 seconds) as the initial hardness. The higher the value, the higher the curing speed in the injection molding and the shorter the cycle time. 201211089
>則i值顯示在表2中： 注模後的初 始硬度 Shore A> then the value of i is shown in Table 2: Initial hardness after injection molding Shore A
非根據本發明的對比實施例 f 225B為基質的傳統Tpus相比，本發 =丁二酸u_丙酸醋(分子量為2,2〇〇)為基質的 卿s姐目同配方下具有顯著改進的1GG%模量和对 撕裂擴展性(實施例1-2 ; 3-5 ; ; 8 9)。 在相同1 〇〇%模量下，以分子量為2,9〇〇的聚醋 為基質的TPU具有進—步改進的固化速度(實施例1 和10)，而以非根據本發明並且分子量為^00的聚 酯為基質的對比TPU具有顯著較差的固化速度(實 施例3和4*)。 【圖式簡單說明】 【主要元件符號說明】 無Compared with the conventional Tpus of the comparative example f 225B according to the present invention, the present invention = succinic acid u-propionic acid vinegar (having a molecular weight of 2, 2 Å) as a matrix has a significant Improved 1GG% modulus and tear propagation (Examples 1-2; 3-5; ; 8 9). At the same 1 〇〇% modulus, the TPU with a molecular weight of 2,9 Å has a further improved curing speed (Examples 1 and 10), but not according to the invention and the molecular weight is The polyester-based comparative TPU of ^00 has a significantly poorer cure speed (Examples 3 and 4*). [Simple description of the diagram] [Explanation of main component symbols]